Manufacture of azo dyestuffs



Patented Apr. 27, 1937 ce, assior a Societe Anonyme des Maties Coiorantes & Produits Chimiques de-Saint-Denis, Paris, France, a

company or France No Drawing. Application December 16, 1935, Egegial No. 54.789. In France December 22,

1d @laims.

Mixtures of aryl anti-diazosulphonates or aryl hydrazine-sulphonatm with azo coupling components are stable under ordinary conditions and their solutions do not undergo spontaneous coupling; It is known that these mixtures can be caused to undergo coupling by the action of light (see particularly French Patent No. 760,784) or in the case of certain particular diazosulphonates applied to fibrous material by impregnation, by the action of a steaming operation (see German Patents Nos. 560,797, 563,061, 560,798 and 578,648)

The present invention relates to the production of azo-dyestufis in substance or on a fibre which also makes use of mixtures of coupling components with aromatic anti-diazosulphonates or hydrazine-sulphonates i. e. with aromatic compounds in which a sulphonic group is connected to an aryl group by a dinitrogen group. In accordance with the present invention the mixture is caused to undergo coupling by-subjecting it to the action of an energetic oxidizing agent and then, if required, to the action of an alkaline agent.

The invention is of special importance in its application to the production of insoluble azodyestufis on textile fibres. For this purpose there are used diazosulphonates or hydrazine-sulphonates prepared from aromatic amines which are free from groups which impart solubility, such as COOH or $0311 and coupling components which, are likewise free from these groups. Since the coupling components generally contain hydroxyl groups which render them soluble in alkaline media, an alkaline solution of the' mixture can be used for the impregnation of the fibre. This impregnation may extend throughout the material or may be only local so that after development there will be produced a dyeing or a print respec tively. The solutions may, of course, contain all the known ingredients which are used in dyeing and printing and especially in the production of insoluble azo-dyestufis on fibrous materials by means of a single mixture containing the two coupling substances (rapid solid dyestuffs, rapidogens,

, dyestufis obtained with the aid of nitrosamines) The course of the process is quite unexpected for it was to be supposed that the oxidizing agent would first attack the azo-coupling components which are readily oxidized and would thus render coupling impracticable.

The dyestufi may be formed actually in the course of the oxidation or it may be formed in a subsequent treatment, generally an alkaline treatment which itself may be conducted in a. liquid or gaseous medium. In order to prepare the dyestuif in a single stage the oxidation may be conducted at a temperature higher than ordinary temperature; thus the dyestufis may be formed on the fibre by treating the fibre impregnated with the selected mixture with a halogen in presence of hot water or steam.

The diazosulphonates or hydrazine-sulphonates which are best suited for carrying out the invention are those-which are prepared from feebly basic aromatic amines containing in the molecule a negative substituent such as a nitro-group or halogen and so on. 4

For the production of azo-dyestufis on fibrous material in accordance with the invention there are advantageously used azo-components of the type hitherto used industrially for a like purpose, such as the arylides of organic acids capable of coupling, particularly the arylides of B-oxynaphthoic acid, of 2-hydroxyanthracene-3-carboxylic acid, of oxycarbazole and oxynaphthocarbazole carboxylic acids, of carboxylic acids having a coupling position in a methylene group which may or may not form part of a ring, such as acyl acetic acids, aroyl acetic acids and so on.

Insoluble azo-dyestufis can be produced in accordance with the present invention on the various animal and vegetable fibres and on artificial fibres of regenerated cellulose, cellulose ethers or cellulose esters.

The following examples illustrate the invention, the parts in Examples 6 and 7 being by weight:

Example 1 A cotton fabric isprinted with the following mixture: Y

Grams Sodium 2-methyl-5-chlorobenzene diazo-sul- After the material has been dried it is treated for 3 seconds in an apparatus containing steam and chlorine at 100 C. in order to develop the dyeing. Then the fabric is washed and treated in a boiling bath containing soap and sodium carbonate. There are obtained beautiful red prints.

Like prints are obtained by printing the same mixture on fabrics of artificial silk of viscose or acetyl cellulose, or natural silk or wool.

By replacing the two components in the foregoing example by other diazosulphonates and coupling components there are obtained the shades indicated in the following table:

Coupling component: Dlazosulphonate (2'-h droxy-W-naph- Shade they Sodium z-metlioxy-a-ni- Aminobenzene... Bluish bortrobenzenediazosuldeaux. pbonate.

D 1-amino-225-dimeth- Do.

cry-benzene. i-amino-a-nitroben- Do.

zene. l-arnino-z-methylben- Do.

zene. Do l-amino-Z-methoxy- Bordeaux.

benzene. Do Lamina-l-methoxy- Bluish borbenzene. deaux. Do-. 2-aminonaphthalene..- Do. Do 1-amino-2-methyl-4- Do.

chlorobenzene.

Bedlam 2-n ifl-4 mflii y aminobenzene Biuish red. benzene diazosulphonate.

Do 1-amino-2:5-dimetii- Red.

oxy-benzene.

Do l-amino-ii-nitroben- Binish red.

zone.

Sodium 2nlt -4-m i7 1-amino-2-methyl- Very bluish nz diawwlpho benzene. red. na

D0 1-amino-2-methoxy- Red.

benzene.

D0 1-amino-4-methoxy- Very bluish benzene. red.

sodium z-lflll'flfllefllyl- 2-aminonaphthaiene... Red.

beitiezene diezosulpho na D0 1-nmino-2-methyl- Very bluish benzene diazosuipho- 1-amino-225-dimeth Orange red.

oxy nzene. 1 amino 2 metbyl- Do.

benzene. 1 amino 2 methoxy- Do.

benzene. 1 amino 3 nitro- Red.

benzene. 1 amino 4 methoxy- Orange red. I benzene. Sodium 3- h1 9- -1 Bfl y Aminobenzene Yeliowish red.

benzene diazosulpho- [l8 0- Do 1-emine-2z5- dimetii Yellowish red.

oxybenzene. Do 1 amino 3 nitro- Brownish red.

benzene. Do 1 amino 2 methyl- Bright red. benzene. Do 1-amino-2-methoxy- Yellowish red.

benzene. Do.. 1 amino 4 methoxy- Scarlet. Sodi m 2 5 di m cben fi o a 11 I 0 0! mino nzene ran 0 re zene diazosulphonate. 8

Do 1-amino-2z5-dimetb- D u l l r e d oxybenzene. orange. Do 1 amino 3 nitro- D u ll orange benzene. 7 re 1-amino-2-methyl- Bright red benzene. orange. 1 amino- 2- methoxy- Orange red.

benzene. l-amino-4-methoxy- D u ll orange DZSDO. Sodium a-nitro-e-methoxy- 1-amino-2:5-dimeth- Dull red.

benrenediazosulphonate. a ry-benzene.

Do... i-emino-a-nitrobenzene. Banish red. Do l-amino-z-metbylben- Yeilowish red.

zene. Do i-amino-2-methoxy- Bright bluish benzene. scarlet. Sodium 2-nitrobenzenc- Aminobenzene Red orange.

diazosulphonate. I

Do 1-amino-2:5-dimeth- Dull red oroxy-benzene. cage;

r Bluish scarlet.

Coupling component Dinzosulphonate (2'4: roxy-3'-neph- Shade they)- Sodium Z-nitrobenzene- 1-arnino-2-methylben- Yeliowish red.

tro benzene diazosul amino)-3:3 i-

diazosulphonate. zene.

Do l-amlno-2-metboxy- Red orange. benzene.

Dlazosulphonate Coupling component Shade Sodium 2-methoxy-4-nitrol-(2-hydroxyanthra- Bluisli black hen z en e-diazosulphocene -3 carboylamviolet. nate. inol-Q-meth y i b e n zene.

Sodium 2-nitro-4-methyl- ....-.do Brown red.

benzene-diazosulphcnate.

Sodium 3-nitro-6-methyl- .--..do Duiivioiet.

benzene-diazosulphonate.

Sodiuin3-chloro-e-methyl- .-...do Do.

benzenediazosulphonate.

Sodium 2:5-dichloroben- Ydr0Xyanthra- Brown.

zene diezosulpbonate. cene-3'-carbo lamino)-2-methy -benzene.

Sodium 3-nitro-B-methoxy- .....do Dull violet.

benzene diazosulphonate.

Sodium Q-methoxy-l-nitro- 1-(2'--hydroxyeerba- Brown red.

benzene diazosulplionate. zole-3-car y ino-4-chlorobenzone.

Sodium 3-nitro-fi-methyl- Yellow brown.

benzene dinzosuiphonate.

SodiumSchloro-G-methyibenzene diazosulfabonate.

Sodium median oi-oben- 1- (2 y w r a- Ye w b zene-diazosulphonate. Z r g amino-4-chioro nzene..

$0dillm3-nitro-6-methoxydo Brown.

benzene diazosulphonate.

odium Z-nitrobenzene- .--..d0 D0- diazosuiphonate.

Sodium 2-methoxy-4-nli-(3"- y y-7':8 Yellow ish trobenzene diazosulbenzocarbazol-2-'- g phonate. carboylamino)-4- methoxybenzcne.

Do 1-(3-hydroxy-7':8'- Grey.

benzocarbazol-2"- carboylamino)-2- methoxy-s-methyl- A benzene.

sodium 2-nitro-4-methyldo Yellowieh betnzene-diazosulphog na e.

Sodium a nitro-n-methyl- ..do Reddish black betnzene-diazosulplioviolet. na 0.

Sodium 2-methoxy-4-ni- 4:4 -di(acetoacet 1- Yellow.

phonate. methyl-diphenyl. Sodium 2-nltro4-methyl- ..do Reddisb yelbenzene-diazosulpholow.

n e. Sodium S-nIt ro-(i-methyl- .....do Yellow.

benzene-dlazosulphonate. Sodium S-chlorodmeth- .-.--do D0.

vl-genzene-diazosulphonn Sodium 2-nitrobenzene- ..do Brownish yeldiazosulphonate. low. Sodium 2:5-dichloroben- 2-hydroxynephthalcne Orange.

zene-diazosulphonnte. Sodium 2-nltrobenzene- ...do Orange red.

diazosulphonate.

Example 2 A cotton fabric is printed with the following mixture:

Sodium 2-nitrobenzene-diazosulphonate- Grams 15 1 (2' hydroxy 3' naphthoyl) amino 2 methylbenzene 15 Caustic soda solution of 40 B 14 Starch tragacanth thickening 500 Water 412 water.

'sulphonate, 0.8

By using in the printing preparation sodium 2 -dichlorobenzene-diazosulphonate and 1- (2'- hydroxy-3'-naphthoyl) amino-Z-methylbenzene and developing the dyeing. by means of a boiling salt solution of 20 percent strength through which chlorine is passed there are obtained yellowish-scarlet prints.

Example 3 If in Example 1 the sodium 5-chloro-2-methylbenzene-diazosulphonate is replaced by the corresponding quantity of S-chloro-Z-methylbenzerie hydrazine sulphonic acid and the operation is conducted otherwise as therein prescribed there are obtained prints of the same shade.

Example 4 Printing is conducted as in Example 1 but with the use of sodium 2-methoxy-4-chlorobenzene diazos ulphonate and thoyl)-amino-2-methoxybenzene. The dyeing is developed by passing the moist material during several seconds first through an atmosphere of chlorine and then through an atmosphere of ammonia or through a solution of sodium carbonate. Red prints are obtained.

Example 5 A cotton fabric is impregnated with the following preparation:-

Grams Sodium 2-methyl-5-chlorobenzene diazosulphonate 20 1 (2' hydroxy- 3- naphthoyl) amino -2 methylbenzene 20 Alcohol 20 Caustic soda solution of 40 B 20 Glycerine 50 Tragacanth mucilage of 6 per cent strength- 100 Water 770 The material is dried and treated as described in Example 1 to develop the dyeing. A beautiful red dyeing is thus obtained.

Example 6 A current of chlorine is passed slowly through a cold solution prepared'from parts of sodium 2-methyl-5-chlorobenzene diazosulphonate, 10 parts of 1-(2'-hydroxy-3'-naphthoyl) -amino-2- methylbenzene, 10 parts of alcohol, 10 parts of caustic soda solution of 40 Be. and 960 parts of water. There is at once formed-a red precipitate which gradually increases in bulk. when no further precipitation occurs the current of chlorine is interrupted and the dyestufi is filtered and dried.

Example 7 A solution is prepared by dissolving 1 part of sodium 2-hydroxy-naphthalene-6-sulphonate, 1 part of sodium 2-methyl-5-chlorobenzene diazopart of sodium bicarbonate and 2 parts of sodium chloride in 100 parts of water and a current of chlorine is passed through the solution. There is at once precipitated an orangered dyestufi which is isolated by saturating the solution with salt and filtering. The dyestufi is identical with that obtained by the direct action of 2-methyl-5-chlorobenzene diazonium chloride on sodium 2-hydroxynaphthalene-6-sulphonate. It dyes wool .an orange shade.

The diazosulphonates referred to herein may be prepared by any suitable process and particularly in the manner indicated in French Patent No. 760,784.

What I claim is:

l. A method of manufacturing azo-dyestufis,

which comprises, treating with an oxidizing which comprises, treating with an oxidizing agenta mixture of an azo-coupling component and a salt of an aryl hydrazine sulphonic acid.

4. A method of manufacturing azo-dyestufis, which comprises, treating a mixture of an azocoupling component and a salt. oi'a sulphonic derivative of an aryl compound, in which the sulphonic group is connected to the aryl nucleus through a dinitrogen group, with an oxidizing agent and subsequently with an alkaline agent.

5. A method according to claim 1 in which said salt contains in the nucleus an electronegative group.

6. A method according to claim 1 in which said salt contains in the nucleus a halogen group.

7. A method according to claim 1 in which said salt contains in the nucleus a nitro-group.

8. A method according to claim 1 in which said coupling component is an arylide of an organic acid capable of coupling.

9. A method of producing insoluble dyestufls on fibrous material, which comprises, impregnating said material simultaneously with an oxidizing agent and a mixture of an azo-coupling component and a salt of a sulphonic derivative of an aryl. compound in which the sulphonic group is connected to the aryl nucleus through a dinitrogen group, neither of these components including a solubilizing group apart from said sulphonic group, and treating said, impregnated fibrous material with a halogen in the presence of Water.

10. A methodaccording to claim 9 in which said water is in the form of steam.

11. A method for producing water insoluble azo-dyestuffs on a fibrous material, which comprises applying to said fibrous material a. mixture including an azo-coupling component and a salt of a sulphonic derivative of an aryl compound in which the sulphonic group is connected to the aryl nucleus through a dinitrogen group, neither of said azo-coupling component and said salt including a water solubilizing group apart from said sulphonic group, and subjecting said mixture on the fibrous material to the action of an oxidizing agent.

12. The method of claim 11, further comprising subjecting said mixture on the fibrous material to a subsequent treatment with an alkaline agent.

13. A method of dyeing a fibrous material which comprises applying to said fibrous material an alkaline mixture including an azo-coupling component and a salt of a sulphonic derivative of an aryl compound containing at least one hydroxyl group, in which the sulphonic group is connected to the aryl nucleus through a dinitrogen group, neither of said azo-coupling component and said salt including a water solubilizing 7 group apart from said sulphonic group, and subjecting said mixture on the fibrous material to the action or an oxidizing agent.

14. The method of developing a. normally stable mixture of an azo-coupling component and a salt 5 of a suiphonic derivative of an aryl compound in which the sulphonic group is connected to the 

